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WO1988000199A1 - Nouvel ester de thiophosphate ainsi que mousse de polyurethane ou prepolymere contenant du tri- et du bi-(2,4,6-tribromophenoxy) (thio) phosphate - Google Patents

Nouvel ester de thiophosphate ainsi que mousse de polyurethane ou prepolymere contenant du tri- et du bi-(2,4,6-tribromophenoxy) (thio) phosphate Download PDF

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Publication number
WO1988000199A1
WO1988000199A1 PCT/AU1987/000212 AU8700212W WO8800199A1 WO 1988000199 A1 WO1988000199 A1 WO 1988000199A1 AU 8700212 W AU8700212 W AU 8700212W WO 8800199 A1 WO8800199 A1 WO 8800199A1
Authority
WO
WIPO (PCT)
Prior art keywords
prepolymer
compound
mixture
formula
tribromophenoxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/AU1987/000212
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English (en)
Inventor
Richard John Maerschel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to KR1019880700260A priority Critical patent/KR880701725A/ko
Publication of WO1988000199A1 publication Critical patent/WO1988000199A1/fr
Priority to NO881042A priority patent/NO881042D0/no
Priority to DK128088A priority patent/DK128088D0/da
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/18—Esters of thiophosphoric acids with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5398—Phosphorus bound to sulfur

Definitions

  • This invention relates to compounds, processes and products.
  • this invention relates to broninated phenol esters and to their use in mixtures with prepolymers in order to improve certain characteristics of materials to be synthesized from such prepolymers.
  • An additive of this invention is one compound or a mixture of compounds chosen from a group of brominated phenol esters which ha ve exhibited f ire retardent , surf actant and plasticising properties.
  • a method of producing fire retardent polyurethane foam wherein the additive is mixed into either an isocyanate prepolymer or a polyol prepolymer of the polyur ⁇ thane system, and the modified prepolymer thus formed is in turn mixed with polyol prepolymer or isocyanate prepolymer respectively to produce polyurethane foam.
  • the present invention provides a polyurethane foam containing a fire retarding amount of a mixture of a compound of formula XI set out in the accompanying drawings and a compound of formula XII set out in the accompanying drawings wherein X 1 and S 2 are oxygen or sulphur and RO- is 2,4,6-tribromophenoxy.
  • the present invention also provides a polyurethane foam prepolymer containing a fire retarding amount, with respect to a foam which can be produced, of a mixture of a compound of formula XI set out in the accompanying drawings and a compound of fornula XII set out in the accompanying drawings wherein X 1 and X 2 are oxygen or sulphur and RO- is 2,4,6- tribromophenoxy. Preferably X 1 and X 2 are both oxygen or both sulphur.
  • the foam or prepolymer may additionally include a compound of formula V set out in the accompanying drawings.
  • the prepolymer may be a polyol or isocyanate. The latter is preferred.
  • the prepolymer preferably comprises an organic base.
  • That base is preferably selected from triethylamine, ethylene diamine, and triethano 1 amine.
  • said compound of formula XI is present in said mixture as from 70 to 80%.
  • said compound of formula XII is present in said mixture as from 20 to 30%. by weight.
  • said compound of formula XIII is present in said mixture as from 3 to 8% by weight.
  • said mixture is present in said prepolymer as from 21 ⁇ 2 to 20 preferably 8 to 10% by weight.
  • said organic base is present in said mixture as from 6 to 8% by weight.
  • the present invention also provides the compound of formula II set out in the accompanying drawings wherein RO- is 2,4,6 -tribromophenoxy and mixtures containing same.
  • the present invention provides in a preferred aspect for use of five brominated phenol esters with compound of formulae I-V set out in the accompanying drawings.
  • Compound II which is the preferred component of the additive does not seem to have been previously described.
  • Compound IV as a fire retardent does not seem to have been described.
  • One previous publication [Benbow & Cullis (1975), Combustion and Flame, v.24, p.217-230] describes the use of Compound III for fire retardation of flexible polyurethane foam. Its use was considered by those authors to be unsatisfactory, primarily because of poor solubility.
  • the acidity introduced by either Compound II or I V partly neutralizes amine catalysts in the system resulting in a reduced rate of foaming when polyol and isocyanate are mixed.
  • This ef f ect may be at l east in part reduced by addition of an organic base, severa l of which ha ve been tested successful ly.
  • a t t empera tur es pr oduced b y a n exoth ermic react ion when isocyanate and polyol prepolymers are mixed, isocyanate is released to recombine immediately with hydroxyl residues to f orm the urethane l inkages.
  • the diester (Compound II or I V) is not onl y ful ly solubil ized but also helps to solubilize the triesters, both phosphate (Compound I or III) and phosphite (Compound V), possibly by pi-bonding.
  • the f ol lowing example provides a process f or manufacture of the additive.
  • the esters were manufactured in acetone solution by esterif ication of bromol (2,4 ,6- tribromophenol) produced in situ from phenol.
  • EXAMPLE In a first procedure, phenol in acetone was mixed with bromine (1:5.2 phenol/bromine w/w) to form bromol, then this mixture was mixed with phosphorus tribromide (1.05:1 pheno 1 /b romi de w/w) at a temperature betwen 15°C and 30°C, thus forming a solution of tribromol phosphite.
  • the initial phenol concentration in acetone was about 80£ w/w, but this value was not critical and was sometimes varied widely according to the mechanics of mixing. This solution was stored under nitrogen until used.
  • phenol in acetone was mixed with thiophosphoryl bromide in bromine solution while controlling the temperature to below 30°C.
  • Reactant ratios were 1:5.2:1.05-1.09 (w/w/w phenol/bromine/bromide), this forming a mixed solution of tribromol thiophosphate (70-80% ) with the balance being dibromol thiophosphate.
  • This solution was then blended with the phosphite solution from the first process (20:1 w/w phosphate/phosphite) and an amount of organic base (triethylamine) sufficient to neutralize 85-95 ⁇ of residual acidity.
  • This mixture was then poured into water whereupon a white flocculated precipitate separated immediately. This precipitate was then dried to reduce water content below 5 i w/w.
  • the final mixture then became Compounds I/II/V (approx. 15/5/1).
  • Those other characteristics include (1 ) enhanced surfactancy of isocyanate prepolymer which tends to improve cell structure and to reduce or remove the need for silicone, (2) improved adhesion to substrate expected from lowering of silicone addition, (3) reduced need for polymerization catalysts, and (4) anticipated marked suppression of embrittlement and catastrophic failure caused by normal or premature aging.
  • Compounds I and II are superior to Compounds III and IV with respect to smoke production, catalysis and solubility, but are inferior with respect to flammability, stability to aerial oxidation and cost.
  • Compound V is a fire and smoke suppressant in its own right but in this application it is provided mainly as an antioxidant for mixing with either of the other compounds to confer long term stability. The effects of each ⁇ f these compounds seemed to be proportional to their content.
  • Type S Bayer Desmodur 44V20 + Bayertherm 4150 (1:1 v/v)
  • Type G Lackfa Lamoltan
  • Type K Bayer Desmodur 44V20: Mixture A (100:16 w/w) + Bayertherm 4150 (1,1 v/v),
  • fixture B performed similarly.
  • Type K is the standard type S a l tered on l y by addition of the additive of this invention.
  • the table represents the direct comparison of commercial ly available standard and premium grade foams with the those provided herein.
  • Values for type S have been arbitrarily set at 10; optimum performance would be zero. Thus, low values are preferred.
  • Both type G and type K behave markedly better than type S. With respect to fire and smoke type K is inferior to type G, but type K is so far superior to type G with respect to structural integrity that its overall performance is significantly better than type G. Type K catches fire and burns at a substantially lower temperature than the other two types.
  • Type K fires are far less dramatic than those of type S, but it is anticipated that in widespread use the most significant advance of type K is to be its relatively low potential to produce those gaseous products which are proven potent killers.
  • Use of polyhalogenated diaryl ethers such as those used in type G is being voluntarily restricted pending availability of satisfactory alternatives because such compounds are known or suspected precursors of di ⁇ xins.
  • Additives ⁇ f the type provided herein have no inherent capacity to produce dioxins at the temperatures anticipated in any combustion possibly sustained by type K foam.
  • These inventions provided herein have contributed to significant advances in the applicability of polyurethane f oam to situations currently precluded because of flammability.
  • These inventions also provide materials with surfactant and plasticising properties which may be of major, rather than incidental, interest in various applications. The claims form part of the disclosure of this specification.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Une mousse de polyurethane se présentant notamment sous forme de prépolymère contient un mélange ignifuge représenté par les formules (XI) et (XII), où X1 et X2 représentent de l'oxygène ou du soufre et RO représenté du 2, 4, 6-tribromophénoxy, ladite mousse comprenant également un nouveau composé représenté par la formule (II), où RO représente également du 2, 4, 6-tribromophénoxy.
PCT/AU1987/000212 1986-07-09 1987-07-09 Nouvel ester de thiophosphate ainsi que mousse de polyurethane ou prepolymere contenant du tri- et du bi-(2,4,6-tribromophenoxy) (thio) phosphate Ceased WO1988000199A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1019880700260A KR880701725A (ko) 1986-07-09 1987-07-09 신규의 티오포스페이트 에스테르; 또한 트리스- 및 비스-(2,4,6-트리브로모페녹시) (티오)포스페이트를 함유한 폴리우레탄 포옴 또는 프레폴리머
NO881042A NO881042D0 (no) 1986-07-09 1988-03-09 Polyuretanskum, forpolymer for dets fremstilling og nye fosfatforbindelser.
DK128088A DK128088D0 (da) 1986-07-09 1988-03-09 Ny thiophosphatester samt polyurethanskum eller praepolymer, der indeholder tris- og bis-(2,4,6-tribromphenoxy)(thio)phosphat

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
AUPH681086 1986-07-09
AUPH6810 1986-07-09
AUPI093887 1987-03-17
AUPI0938 1987-03-17

Publications (1)

Publication Number Publication Date
WO1988000199A1 true WO1988000199A1 (fr) 1988-01-14

Family

ID=25643124

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU1987/000212 Ceased WO1988000199A1 (fr) 1986-07-09 1987-07-09 Nouvel ester de thiophosphate ainsi que mousse de polyurethane ou prepolymere contenant du tri- et du bi-(2,4,6-tribromophenoxy) (thio) phosphate

Country Status (8)

Country Link
EP (1) EP0275280A4 (fr)
JP (1) JPH01500908A (fr)
KR (1) KR880701725A (fr)
DK (1) DK128088D0 (fr)
ES (1) ES2004771A6 (fr)
GR (1) GR871082B (fr)
PT (1) PT85297B (fr)
WO (1) WO1988000199A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GR890100003A (el) * 1988-01-04 1994-03-31 John Richard Maerschel Ενωση ή μίγμα βρωμίου-φοσφώρου-βορίου.

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1401863A (en) * 1972-11-02 1975-08-06 Gen Electric Flame retardant polyester resin compositions
AU6873881A (en) * 1980-03-26 1981-10-01 Dow Chemical Company, The Polymeric isocyanate containing acid phosphate
EP0069975A1 (fr) * 1981-07-15 1983-01-19 BASF Aktiengesellschaft Procédé pour préparer des mousses ignifuges contenant des groupes polyuréthane et/ou polyisocyanurate
US4477600A (en) * 1983-09-23 1984-10-16 Stauffer Chemical Company Polyurethane foams having low scorch discoloration
WO1984004314A1 (fr) * 1983-05-04 1984-11-08 Gen Electric Melange polymere possedant des proprietes de retardement de flamme, indique pour etre utilise dans l'extrusion d'isolation de cable, utilisant de l'oxyde de polyphenylene et un cable electriquement conducteur
EP0189644A2 (fr) * 1985-01-25 1986-08-06 Akzo N.V. Mousse de polyéther-uréthane thermolaminable
US4649163A (en) * 1984-12-07 1987-03-10 Takeda Chemical Industries, Ltd. Flame-retardant polyurethane foam and polyol composition therefor

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2857308A (en) * 1956-11-15 1958-10-21 Monsanto Chemicals Method of destroying nematodes employing phosphorodithioates
US4021406A (en) * 1973-05-21 1977-05-03 M & T Chemicals Inc. Flame retardant compositions
US4059655A (en) * 1975-11-24 1977-11-22 Ppg Industries, Inc. Process for preparing halogenated diaryl hydrogen phosphates
JPS53122817A (en) * 1977-03-30 1978-10-26 Teijin Ltd Wholly aromatic polyamide fibers having improved flame resistance

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1401863A (en) * 1972-11-02 1975-08-06 Gen Electric Flame retardant polyester resin compositions
AU6873881A (en) * 1980-03-26 1981-10-01 Dow Chemical Company, The Polymeric isocyanate containing acid phosphate
EP0069975A1 (fr) * 1981-07-15 1983-01-19 BASF Aktiengesellschaft Procédé pour préparer des mousses ignifuges contenant des groupes polyuréthane et/ou polyisocyanurate
WO1984004314A1 (fr) * 1983-05-04 1984-11-08 Gen Electric Melange polymere possedant des proprietes de retardement de flamme, indique pour etre utilise dans l'extrusion d'isolation de cable, utilisant de l'oxyde de polyphenylene et un cable electriquement conducteur
US4477600A (en) * 1983-09-23 1984-10-16 Stauffer Chemical Company Polyurethane foams having low scorch discoloration
AU3337484A (en) * 1983-09-23 1985-03-28 Stauffer Chemical Company Fire proofing with organophosphite and halogenated phosphoric acid ester
US4649163A (en) * 1984-12-07 1987-03-10 Takeda Chemical Industries, Ltd. Flame-retardant polyurethane foam and polyol composition therefor
EP0189644A2 (fr) * 1985-01-25 1986-08-06 Akzo N.V. Mousse de polyéther-uréthane thermolaminable

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0275280A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GR890100003A (el) * 1988-01-04 1994-03-31 John Richard Maerschel Ενωση ή μίγμα βρωμίου-φοσφώρου-βορίου.

Also Published As

Publication number Publication date
ES2004771A6 (es) 1989-02-01
EP0275280A4 (fr) 1988-11-16
DK128088A (da) 1988-03-09
EP0275280A1 (fr) 1988-07-27
PT85297B (en) 1989-10-12
GR871082B (en) 1987-11-12
PT85297A (en) 1987-08-01
KR880701725A (ko) 1988-11-04
JPH01500908A (ja) 1989-03-30
DK128088D0 (da) 1988-03-09

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